Denaturant



. Feb. 27, 1

UNITED STATES.

' PATENT QFF-ICE DENATUBAN'I John C. Woodhouse, Cragmere, Del, assignor to E. I. du Pont de Nemours a Company, Wilmington, Del, a corporation of Delaware lWo Drawing. Application December 18, 1937,

Serial No. 180,584

SGIaims.

that it cannot be diverted from'its intended use or can readily be identified or both. For example, this procedure has been applied to methanol to avoid its being taken internally, as well as to ethanol and other alcohols which might otherwise be diverted from their intendedcommercial use to that oi. a beverage. substances such as ethyl acetate, and other esters, which might fairly easily be otherwise converted to alcohols and thus diverted from their intended use, have likewise been denatured. Upon chemical treatment of such esters, the denaturant has been intended to carry over to the alcohol and cause itto be unpotable. Y

Materials which have been proposed as de naturants before have had one or more characteristics which adapt them for denaturing purposes. There are, however, several specialjeatures which it is desirable to have in a denaturant and all of which have not been possessed to. a sumcient degree by many of the denaturants previously suggested. Thus, for example, it is de-' sirable that a denaturant have an obnoxious taste and a distinctive-odor. Substances have been proposed previously which possess disagreeable tastes but the odor carried by the denaturant has often been of such a character as to make the final denatured alcohol commercially undesirable. v

Another characteristic which a denaturant must possess is that of difliculty of removal from the denatured medium. As rapidly as denaturants have been proposed, methods have been discovered for their removal from the denatured medium. The methods utilized for'removal of denaturants have been usually chemical treatment of the denatured medium combined with or followed by various distillation steps and further chemical treatment until, finally, relatively pure alcohol has been obtained.

It is an object of the present invention to overcome the disadvantages of the prior art and to provide a new. and improved denaturant and denatured materials.

It is a further object of the present invention to provide a denatured ethyl alcohol which possessses a distinctive but unobjectionable odor, and a taste which renders the ethyl alcohol unpotable.

' Similarly,

(cl. zoz-s' n Other objects and advantages of the present invention will be apparent by reference to the following specification in which the preferred embodiments and details are set forth.

According to the present invention a denatured 5 v material from which it is extremely diilicult if not impossible to remove the denaturant is prepared by mixing' with liquid materials such as gasoline, an ester such as ethyl acetate, an aland propyl and the like, relatively small quantities of a substituted ketone of the general formula:

'cohol, including such alcohols as methyl, ethyl,

containing only the elements carbon, hydrogen,

and oxygen, boiling in the range of from 100 to 200 C. and in which R1 and R2 are saturated or unsaturated acyclic, isocyclic, or heterocyclic groups and in which either or both R1 and R2 are substituted by oxygen or hydroxyl.

The denaturants of this invention are generally applicable for treatment of any normally liquid material which it-is desired to denature although, preferably, the material to be denatured should have a boiling point in'the range of C. to 250 C. From a material having a boiling point in this range it will be found extremely diflicult, it not impossible, to remove my denaturant.

My denaturants are also adapted to and effective in denaturing and distinguishing motor fuels from one another in. cases, for example, where it is desired to identify and keep separate individual supplies or stocks of gasoline. Specifically, a

other according to this invention, such, for example, as methyl alcohol, ethyl alcohol, butyl al- 40 cohol, isobutyl alcohol, isopropyl alcohol, and others. Similarly, a large number of esters may be successfully denatured or distinguished from one another, substantially the only requisites being that the ester. should have a. boiling point 4 in the range above indicated and, further, the ester should be one which might be fairly easily transformed into an alcohol. Thus, for example,

in addition to denaturing ethyl esters such'as ethyl acetate mentioned before, the denaturants of this mates, propionates, butyrates, isobutyrates and like esters.

3 substituted ketones possess a characteristic odor and are unpotable because of odor and taste. Both the odor and the taste persist in Example 1 An unpotable ethyl alcohol .was.

adding 0.2 volume'of acetylcaproyl,

(H3.C0.CO.(CH4)4-CH3, B. P. 1'12" 0.) to 99.8 volumes 01' pure 95% ethyl alcohol.

Example 2 An unpotable denatured alcohol was prepared by adding 5 cc." of 2-methyl-2-hydroxy-3-butaprepared by tcihmomxcmyoqcm, B. R. 139'i-14'0 Q).

- to 100 cc.'o1' pure 95% ethyl alcohol.

E am e 3 g V 160 cc. of a denatured alcohol, prepared by mixing .100 volumes 01' pure 95% .ethyl alcohol i and 5 volumes of diacetyln 4 .(c'mcacocm, B. R. saw-sac c);

was mixed with 160 cc. oi water and 480 cc. of saturated salt solution. The clear solution was shaken 3 minutes with 40 cc. of white'oil and allowed to stand overnight. The alcoholic brine layer was thenseparated from the white oil and shaken '3 minutes with a new charge of 32 cc. white oil. After standing an hour the lower layer was removed and'treated with '8 g. of activated charcoal for 30 minutes at room temperature. The mixture was filtered and the filtrate treated with an additional 8 g. of activated charcoal for 30 minutes at-room temperature. The filtrate from the second charcoal treatment was distilled using a theoretical plate column and a drawoiI rate of ice. per minute. Eight 16 cc. cuts were collected. All cuts had a yellow color and were unpotable.

Example 4 A denatured alcohol, prepared by adding 5 cc. of 1-hydroxy-2-methyl-butanone-3.

(CHJ-CO-CH(CHJ) .CEOH;

B. R. 83-80 (L/10mm),

to 100 cc. of pure 95% ethyl alcohol, was treated by the procedure of Example 3. The distillate from the distillation was unpotable.

Example 5 100 cc. of denatured alcohol, prepared by add--- 7 ing 4 volumes of acetyl methyl carbinol,

. (CHs.CO.C(OH).CHs, B. P. 142' OJ,

to 100 volumes of pure 95% ethyl alcohol, was mixed with 225 cc. of saturated salt solution,

75 cc. of water and cent white oil. The

mixture was shaken. 2 minutes and allowed to stand 1 hour. The alcoholic brine layer was separated from the oil'layer and extracted with 'a second 25 cc. portion of white oil. The alcoholic brine from the second extraction was mixed.

minutes. The mixture was filtered and" treated unpotable.

:1 volume of acetyl methyl 'carbinol to 100 volumes of gasoline. a

r with a second 5 g. portion oil activated carbon.

The filtrate from the second carbon treatment was mixed with 1 g. of sodium carbonate ;and 1 g. of calcium hypochlorite. This mixture was refluxed for minutes and then distilled using i a column of approximately 15 theoretical plates, a reflux ratio oi. approximately 10:1 and a drawoil. rate of 1 cc. per minute. The distillate had the odor and taste of the denaturant and was 11 Example 6 A denatured alcohol,, prepared by adding 4 volumes of acetylacetone to 100 volumes of pure 95% ethyl alcohol, was treated by the procedure of Example 5 except that toluene was used as i the extracting agent instead of white oil. The

distillate from the distillation had the ,odor and taste of the denaturant and wasunpotable.

. Example 7 a 1 25 cc.'oi denatured alcohol, prepared by adding 1 volume acetylacetone to 100 volumes of pure 95% ,ethyl alcohol, was mixed with 625- cc. of sodium hydroxide. The mixture was refluxed ,30 minutes and then distilled as in Ex- .ample' 5. The distillate had. the odor and taste A denatured ethyl acetate was prepared by adding 1 volume of diacetyl to 100 volumes 01' pure 99% ethyiacetate.

Example 10. A denatured gasoline was prepared by adding Although not indicated in the examples above given, the materials of the present invention may be admixed with other denaturing materials, such, for example, as sulfur-containing materials, wood oil products, and other known denaturing materials. It may be desirable, from time to ,time, to add other denaturing materials which possess stronger and more disagreeable odors than the denaturants oi'the present invention as a method oi distinguishing the denatured material utilised from other denatured materialsor for other-reasons. The denaturants oi the present invention are miscible, however, with anything. generally speaking, with which ethyl alcohol is miscible: and may, thereior'e be utilined in conjunction with other denaturing ma- .terials generally, such as illustrated by the 101- lowing additional examples which show reprea sentative, preferred mixtures.

' Example 11 H A completely denatured alcohol was prepared by adding to100 parts by volume of ethyl alcohol, two parts methyl isobutyl ketone, two I parts of diacetyl' and one part of the sulfur-containing residues obtained in the refining '01 petroleum and known under the name of Agdlte- Example 12 0 e v I 7 An unpotable alcohol was prepared by adding to partsby volume 95% ethyl alcohol two pariaoi' acetyl acetone, threepartsofamlxture oi'primaryandsecondaryaliphatichigheriso alcohols and higher'brauched chain hatches (known under the name of Denol"),-and one part of gasoline denaturant described and claimed in my copending application S. N. 143,295, comprising a mixture of methyl alcohol, higher branched chain ketones and saturated and unsaturated hydrocarbons.

Example 13 An unpotable alcohol of undesirable taste and distinctive odor was prepared by adding to 100 parts by volume of 95% ethyl alcohol, two parts of 2 -methyl2-hydroxy-butanone-3 and four parts of the mixture of pyroligneous bodies, free from methanol, produced by the destructive distillation of wood.

Although the several examples illustrate the use of a variety of substituted ketonesaccording to this invention, other substituted ketones may equally as well be substituted therefor, such for example, as 2-methyl-pentadiene-3A; methylpropyl diketone; 2 methyl hexandione-4-5; butanol-3-one-2; heptadione-3, 4; butanol-lone-2; hexadione-2,5, and the like.

The proportions utilized according to the present invention may vary from a very small quantity, such as one-tenth of one per cent, up to ten per cent by volume or more of the alcohol,

' or other material, which is to be denatured, the

scientifically undesirable inasmuch as the char-.

acter of the denatured material is not changed by the incorporation of my denaturant.

Various changes may be made in the present" invention without departing therefrom or sacrificing any of the advantages thereof.

I claim:

1. A denatured alcohol containing denaturing quantities of a substituted ketone selected from the group consisting of acetyl methyl carbinol, butanol-3-one-2, l-hydroxy-2-methyl butanone- 3, 2-methy1-2-hydroxy-3-butanone and butanol- 1-one-2.

2. A denatured alcohol containing from 0.1 to 10% by volume of a substituted ketone selected from the group consisting of acetyl methyl carbinol, butanol-3-one-2, 1-hydroxy-2-methyl butanone-3, 2-methyl-2-hydroxy-B-butanone and butanol -1-one-2.

3. A denatured alcohol containing denaturing quantities of acetyl methyl carbinol.

4. A denatured alcohol containing 01-10% by volume of acetyl methyl carbinol.

5. An alcohol containing acetyl methyl carbinolas a denaturant.

JOHN C. WOODHOUSE.

A great advantage of the present de- 

